CHEM 3411, Fall 2010

Solution Set 1

In this solution set, an underline is used to show the last signicant digit of numbers. For instance in

x = 2.51693

the 2,5,1, and 6 are all signicant. Digits to the right of the underlined digit, the 9 & 3 in the example, are not
signicant and would be rounded o at the end of calculations. Carrying these extra digits for intermediate values in
calculations reduces rounding errors and ensures we get the same answer regardless of the order of arithmetic steps.
Numbers without underlines (including nal answers) are shown with the proper number of sig gs.

1 Exercise 1.2a pg 38
Given
A perfect gas undergoes isothermal compression, which reduces its volume by 2.20 dm3 . The nal pressure and
volume of the gas are pf = 5.04 bar and Vf = 4.65 dm3 , respectively.

In terms of given variables, this is written:

V = Vf Vi = 2.20 dm3

pf = 5.04 bar

Vf = 4.65 dm3

Find
Calculate the original pressure pi of the gas in (a) bar, (b) atm.

Strategy
We begin with the ideal gas law

pV = nRT

We recognize that in this problem the moles of gas n remain constant as well as the temperature T . Therefore the
state of the gas in both the initial and nal state are given by the equations

pi Vi = nRT

and

pf Vf = nRT

respectively. The right hand side of these equations nRT is the same in both.

pi Vi = nRT = pf Vf

and this allows us to relate the initial pressure and volume to the nal pressure and volume by

1
CHEM 3411, Fall 2010
Solution Set 1

p i Vi = p f Vf

(FYI: This equation is Boyles Law.) As the problem asks us to calculate pi well rearrange this equation to

pf Vf
pi =
Vi
We know the values for pf and Vf as they were given in the problem. We can calculate Vi as we know the change in
gas volume V and the initial volume Vi .

V = Vf Vi

Vi = Vf V

Vi = 4.65 dm3 (2.20 dm3 )

Vi = 6.85 dm3

We now solve for pi through substitution.



4.65dm 3
5.04 bar
pi = 
3
6.85
dm
= 3.420 bar

This gives us the solution to part (a) with the initial pressure in bar give as 3.42 bar.

Lastly, we can convert from pressure in bar to pressure in atm using the conversion factor of 1 bar = 0.9870 atm.

3.420
bar 0.987 atm
 = 3.370 atm
1bar

Solution

The initial pressure of the gas is (a) pi = 3.42 bar (b) pi = 3.37 atm.

2
CHEM 3411, Fall 2010
Solution Set 1

2 Exercise 1.10a pg 38
Given
The density of air at p = 0.987 bar and T = 27 C is air = 1.146 kg/m3 .
In terms of given variables, this is written:

p = 0.987 bar

T = 27 C

air = 1.146 kg/m3

Find
Calculate the mole fraction and partial pressure of nitrogen and oxygen, pN2 and pO2 respectively, assuming that . . .

(a) air consists only of these two gases.

(b) air also contains 1.0 mole per cent Ar, Ar = 0.01.

Strategy
First lets convert the temperature from Celsius to Kelvin as all ideal gas calculations use absolute temperature.

T [K] = T [ C] + 273.15
= 27 C + 273.15
b = 300.15 K

Youll notice that this problem has not specied any extensive properties (such as mass, volume, or moles), every
given value is intensive (pressure, temperature, density) and the problem additionally asks us for an intensive answer
(partial pressures). To simplify these calculations well consider a specic V = 1.0000 m3 sample of air and this will
allow us to work with extensive units and well nd this easier for this problem.

V = 1.0000 m3

For this nite sample of air we can calculate its mass m from the given density air .

m = air V
1.1460 kg
= m
1.0000 3
1m3

= 1.14600 kg

We can also calculate the total number of moles in this gas sample using the ideal gas law pV = nRT rearranged to
n = pV /RT .

3
CHEM 3411, Fall 2010
Solution Set 1

pV
n =
RT
0.987bar m
 1.0000 3
= 3   mol1 300.15 
8.314 105  m
bar K1
 K
= 39.545 mol

To solve this problem, well want to determine how to allocate this total number of moles n between the moles of
nitrogen and oxygen, nN2 and nO2 respectively. This is represented by the constraint

n = n N2 + n O 2 (1)

Additionally, the total mass of these two gases must sum to the total mass of the air sample m. We can calculate
the mass of each of these two component from their respective molecular weights (MwN2 & MwO2 ) by

mN2 = MwN2 nN2

mO2 = MwO2 nO2

The sum of these two components must equal the total mass of air.

m = mN2 + mO2

Substituting the expressions for mass of each component gives

m = MwN2 nN2 + MwO2 nO2 (2)

Combining this constraint on mass with our moles constraint given by equation 1 we now have two equations for our
two unknowns, nN2 and nO2 , and we can thereby solves for the moles of each gas component.
Rearranging each equation for nN2 gives us

n N2 = n n O 2 (3)

and

m MwO2 nO2
n N2 =
MwN2
setting the right hand sides equal to each other yields

m MwO2 nO2
n nO 2 =
MwN2
which can be solved for moles of oxygen nO2

n m
MwN2
nO2 = Mw 2
1.0000 MwON2

39.545 mol 1.1460

kg
0.028010
kg/ mol
= 0.032020 
mol
kg/
1.0000 0.028010 
mol
kg/
= 9.5622 mol

4
CHEM 3411, Fall 2010
Solution Set 1

With nO2 we can then calculate nN2 using equation 3

n N2 = n nO 2
= 39.545 mol 9.5622 mol
= 29.982 mol

The mole fractions are simply calculated as i = ni /n

nN 2
N2 =
n
29.982 
mol
= 
39.545mol
= 0.75817

nO 2
O2 =
n
9.5622 
mol
= 
39.545mol
= 0.24181

Now that weve calculated the moles of each component, we can determine the partial pressure of each from the ideal
gas law pV = nRT rearranged to p = nRT /V .

nN2 RT
pN2 =
V
 8.314 105 bar 3   
29.982mol m K1
 1
mol 
300.15
K
= 3
1.0000m
= 0.74818 bar

nO2 RT
pO2 =
V
 8.314 105 bar 3  
9.5622mol m K1
 1
mol 
300.2
K
=
m
1.0000 3

= 0.23862 bar

This gives us the partial pressures for part (a).

We can also check our work for this problem by summing the calculated partial pressures and comparing this to the
given pressure.

p = pN2 + pO2
= 0.74818 bar + 0.23862 bar
= 0.98680 bar

This value is within the uncertainty of the given pressure p = 0.987 bar and the small discrepancy can likely be
attributed to rounding errors.

5
CHEM 3411, Fall 2010
Solution Set 1

To solve part (b) we simply add moles of argon nAr as an additional component to the moles constraint from equation
1

n = nN2 + nO2 + nAr (4)

and also to the mass constraint from equation 2

m = MwN2 nN2 + MwO2 nO2 + MwAr nAr (5)

The problem states that the air contains 1.0 mole per cent Ar, which implies

nAr = 0.010n

substituting this expression for nAr into our two new constraints (equations 4 & 5) gives us

n = nN2 + nO2 + 0.010n

and

m = MwN2 nN2 + MwO2 nO2 + MwAr 0.010n

From this points it is straight forward to solve for nN2 and nO2 as we did in part (a) using these two constraint
equations. The found expression for nO2 is

0.9900n mMwAr 0.010n

MwN2
nO2 = Mw 2
1.0000 mol MwON2


1.1460 
kg/
kg0.0100.039940 
mol39.545 
mol
0.9900 39.545 mol

0.028010
kg/ mol
=
 
mol
1.0000 mol 0.032020 kg/
0.028010 
mol
kg/
= 8.386 mol

Moles of nitrogen is then given by

n N2 = n nO2 0.010n
= 39.545 mol 8.386 mol 0.01 39.545 mol
= 30.85 mol

The mole fractions of these components are

nN 2
N2 =
n
30.85 
mol
= 
39.545mol
= 0.7801

nO 2
O2 =
n
8.386 
mol
= 
39.545
mol
= 0.2121

6
CHEM 3411, Fall 2010
Solution Set 1

As in part (a), we can now calculate partial pressure using the ideal gas law in the form p = nRT /V .

nN2 RT
pN2 =
V
 8.314 105 bar 3  
30.85mol m K1 1
mol 
300.15
K
= 3
1.0000
m
= 0.7698 bar

nO2 RT
pO2 =
V
 8.314 105 bar 3  
8.386mol m K1 1
mol 
300.15
K
= 3
1.0000
m
= 0.2092 bar

We can also calculate the partial pressure of argon pAr .

nAr RT
pAr =
V
 8.314 105 bar 3  
0.010 39.545
mol m K1
 1
mol 
300.15
K
=  3
1m
= 0.009868 bar

Again, we can check our work by summing the partial pressures.

p = pN2 + pO2 + pAr

= 0.7698 bar + 0.2092 bar + 0.009868 bar
= 0.9887 bar

This value is found to be very close to the given pressure p = 0.987 bar.

Solution

(a) The partial pressure of nitrogen and oxygen is pN2 = 0.748 bar and pO2 = 0.239 bar
respectively. The mole fractions are N2 = 0.758 and O2 = 0.242.
(b) The partial pressure of nitrogen and oxygen is pN2 = 0.77 bar and pO2 = 0.21 bar
respectively. The mole fractions are N2 = 0.78 and O2 = 0.21.

7
CHEM 3411, Fall 2010
Solution Set 1

3 Exercise 1.22a pg 39
Given
A certain gas obeys the van der Waals equation with a = 0.50 m6 Pa mol2 . Its molar volume is found to be
Vm = 5.00 104 m3 mol1 at temperature T = 273 K and pressure p = 3.0 MPa.
In terms of given variables, this is written:
a = 0.50 m6 Pa mol2

Vm = 5.00 104 m3 mol1

T = 273 K

p = 3.0 MPa

Find
Calculate the van der Waals constant b of this gas.
What is the compression factor for this gas at the prevailing temperature and pressure?

Strategy

As this problem didnt specify a quantity of gas (either in terms of moles or volume) well assume a nite sample of
gas containing 1 mole to simply solving this problem.

n = 1.00 mol
For this quantity we can calculate the volume of gas from the molar volume we were given.

V = n Vm
 5.00 104 m31
= 1.00
mol mol
= 5.00 104 m3

Next, we can analyze the van der Waals equation of state to determine how well solve for b

nRT ( n )2
p= a
V nb V
Here we see that all of the variables were specied except for b and we can therefore simply use this equation to solve
for b.
On rearrangement the following expression for b is found

V RT
b = ( )2
n p + a Vn
5.00 104 m3 8.314 m3
Pa  mol1 273
K1 K
= ( )2
1 mol  + 0.50  6 2  1
3.0 106
Pa m 
Pa mol mol
5.0010 
4 
m 3

= 4.606 105 m3 /mol

8
CHEM 3411, Fall 2010
Solution Set 1

To determine the compression factor we use its denition

Vm
Z=
Vm

where Vm is the molar volume (volume of a mole n = 1 mol) for the gas and Vm is molar volume of an ideal gas at
the same conditions.
Using the given conditions, we can calculate Vm from the ideal gas law with n = 1 and rearranged into the following
form

RT
Vm =
p
8.314 m3
Pa mol1 273
K1 
K
= 
3.0 10 
6 Pa
= 7.566 104 m3 mol1

Using this value and the given molar volume Vm the compression factor is simply calculated as

Vm
Z =
Vm
5.00 104 m3 mol1
=
7.566 104 m3 mol1
= 0.6609

Solution

b = 4.6 105 m3 /mol

Z = 0.66

9
CHEM 3411, Fall 2010
Solution Set 1

4 Exercise 2.4a pg 85
Given
3
A sample consisting of n = 1.00 mol of perfect gas atoms, for which CV,m = 2 R, initially at pi = 1.00 atm and
Ti = 300. K, is heated reversibly to Tf = 400. K at constant volume.
In terms of given variables, this is written:
n = 1.00 mol

3
CV,m = R = 12.471 J K1 mol1
2

pi = 1.00 atm

Ti = 300 K

Tf = 400 K

V = 0 (constant volume)

Find
Calculate the . . .

nal pressure pf
change in internal energy U

heat q
work w

Strategy
To nd the nal pressure pf , we can use the ideal gas law

pi V = nRTi

pf V = nRTf

solving each of these equations for nR/V , which is constant in this process, and equating the expressions gives

pi /Ti = pf /Tf

which can be solved for pf

10
CHEM 3411, Fall 2010
Solution Set 1

pi Tf
pf =
Ti

1.00 atm 400
K
=

300K
= 1.333 atm

To calculate the change in internal energy well use the denition of heat capacity CV
( )
U
Cv =
T V

which leads to the integral

Tf ( )
U
U = dt
Ti T V
Tf
= CV dt
Ti

Additionally, CV can be calculated from the given molar heat capacity.

CV = n CV,m
 12.4716 J K11
= 1.00
mol mol
= 12.472 J K1

As CV is constant in this problem, the integral is easy to calculate

Tf
U = CV,m dt
Ti
Tf

= CV 
Ti
= CV (Tf Ti )
 (400 
K
1

K 300
= 12.472 J  K)
= 1247.2 J

Lastly, we need to determine which portion of this internal energy change was performed by heat q and which portion
was performed by expansion work w. The sum of these two energy transfers equals the internal energy change U

U = q + w

By simply examining the expression for expansion work

Vf
w= pex dV
Vi

its is apparent that no expansion work was performed as the constant volume V = Vf Vi = 0 ensures this integral
equals zero. Hence, there is no expansion work w = 0.

11
CHEM 3411, Fall 2010
Solution Set 1

From this we nd

q = U = 1247 J

Solution

pf = 1.33 atm

U = 1250 J

w=0

q = 1250 J

12
CHEM 3411, Fall 2010
Solution Set 1

5 Exercise 2.9a pg 86
Given
A m = 12.0 g sample of argon is expanded reversibly and adiabatically from Vi = 1.0 dm3 at Ti = 273.15 K to
Vf = 3.0 dm3 .
In terms of given variables, this is written:

m = 12.0 g

Vi = 1.0 dm3

Ti = 273.15 K

Vf = 3.0 dm3

Find
Calculate the nal temperature Tf .

Strategy
For the change in temperature resulting from the adiabatic expansion of an ideal gas, our textbook has given us the
following formula (equation 2.28a on pg 63)

( )1/c
Vi
Tf = Ti
Vf

Additionally, the textbook lists c = 1.501 for argon gas. Therefore the nal temperature is simply calculated as

( )1/c
Vi
Tf = Ti
Vf
( )1/1.501
1.0 dm3
= 273.15 K
3.0 dm3
= 131 K

Solution

Tf = 130 K

13
CHEM 3411, Fall 2010
Solution Set 1

6 Exercise 2.14a pg 86
This problem, as given includes quantities with a pathologically low number of significant figures. In this solution,
additional sig figs are added to these quantities to show an example of such a problem as you would normally encounter
it.

Given
A sample of n = 4.00 mol O2 is originally conned in a Vi = 20.0 dm3 volume at Ti = 2.70102 K and then undergoes
adiabatic expansion against a constant pressure of pex = 6.00 102 torr until the volume has increased by a factor
of 3.00.
In terms of given variables, this is written:

n = 4.00 mol

Vi = 20.0 dm3

Ti = 270 K

pex = 600 torr

Vf = 3.00Vi = 60.0 dm3

Find
Calculate the . . .

heat q
work w
change in temperature T
change in internal energy U
change in enthalpy H

Strategy
As the expansion is adiabatic, we know there is no heat transfer and q = 0.
Next, we can easily calculate the expansion work w as the gas is expanded against a constant pressure. For such an
expansion the work is given by

w = pex V

To use this expression, well convert pressure from torr to pascals

600 
torr 133.3 Pa
 = 79990 Pa
1.000bar

14
CHEM 3411, Fall 2010
Solution Set 1

Then the expansion work is given by

w = pex V
= pex (Vf Vi )
( )
= 79990 Pa 0.0600 m3 0.0200 m3
= 3.2000 103 Pa m3
N
= 3.2000 103 2 m3
m
= 3.2000 103 J

The change in internal energy U can now be calculated from the energy transfer expression

U = q+w
= 0 + 3.2000 103 J
= 3.2000 103 J

This change in internal energy is associated with a change in temperature of the gas. We can calculated this change
from the heat capacity of O2 gas.
( )
U
CV =
T V

The constant volume molar heat capacity Cv,m of O2 can be calculated from this gass constant pressure molar heat
capacity Cp,m as

Cv,m = Cp,m R

From our text book we nd Cp,m = 29.38/uJ K1 mol1 near the temperature range of interest

Tf ( )
U
Um = dt
Ti T V
Tf
= CV,m dt
Ti
Tf

= CV,m 
Ti
= (Cp,m R) T

This expression is for a molar quantity and well thereby need to convert U to molar internal energy Um .

U
Um =
n
3.2000 103 J
=
4.00 mol
= 800.00 J mol1

Thereby T is simply

15
CHEM 3411, Fall 2010
Solution Set 1

Um
T =
Cp,m R
1
J
800.00 mol
= 1 1
J K1
29.38 mol J K1
8.314 mol
= 37.975 K

The nal temperature is

Tf = Ti + T
= 270 K + 37.975 K
= 232.03 K

Lastly, we can calculate the change in enthalpy H from the denition of enthalpy

H = U + (pV )
= U + nRT
 
= 3.2000 103 J + 4.00
mol K
 8.314 J 1 1
mol 
37.975
K
= 4130.3

Solution

q=0

w = 3.20 103 J

U = 3.20 103 J

T = 38.0 K

H = 4.13 103 J

16